Polyester composition with improved dyeing properties

ABSTRACT

A copolymer composition is disclosed with advantages for textile fibers, yarns, blended yarns, fabrics, and garments. The composition includes polyester copolymer, between about 4.5 and 5.5 percent adipic acid based on the amount of copolymer, between about 630 and 770 parts per million (ppm) of pentaerythritol based on the amount of copolymer, and between about 3.4 and 4.2 percent polyethylene glycol based on the amount of copolymer.

RELATED APPLICATIONS

This application is related to Ser. No. ______, filed Sep. 7, 2016 for“Polyester Composition with Improved Dyeing Properties.”

BACKGROUND

The present invention relates to polyester copolymer compositionssuitable for synthetic filaments and to fibers and fabrics that can bemade from such compositions. In particular, the invention relates tocompositions that will produce fibers that can be blended and dyed withcotton under conditions that are more typically favorable for cottonthan for polyester.

The use of synthetic compositions to produce filaments, fibers, and thenfabrics is well established. Accordingly, improvements in suchentrenched compositions can be particularly advantageous. Suchimprovements are, of course, more valuable when they enhance desiredcharacteristics of filaments, fibers, fabrics, and items—very oftenclothing—made from such compositions.

Working backwards, a garment is typically formed of a fabric that iseither woven or knitted from yarns. In turn, yarns are formed fromindividual fibers joined together, most commonly using well known andwell established spinning processes.

Natural fibers—the most common are cotton and wool—have characteristicsthat produce desired properties in yarns, fabrics, and garments. Forexample, wool has (among other advantages) excellent thermal properties,and remains insulating when wet. Unless treated properly, however, woolcan be abrasive and thus uncomfortable when in contact with skin forextended intervals. Cotton produces fabrics that are comfortable andbreathable, but can lose its thermal insulation properties when wet.Further advantages of cotton, wool, and other natural fibers aregenerally well understood in the art.

In the same manner, synthetic fibers have some properties that aresubjectively better then natural fibers, some of which can include(particularly in the case of polyester) strength, durability, and“memory.”

Accordingly, one of the goals in producing or designing or developingsynthetic compositions for eventual use as fibers, yarns and fabrics isto take advantage of some of the favorable properties of synthetics,while matching as closely as possible—or in some cases improvingupon—the desired properties of natural fibers (e.g., the thermalinsulation of wool, but less abrasive; the comfort of cotton, but withbetter thermal properties when wet).

In the clothing industry, the ability to produce garments with desiredcolors is a fundamental goal. The nature of both natural and syntheticfibers and their underlying chemical compositions requires, however,that color be obtained by some type of dyeing process. Depending uponcircumstances, fibers can be dyed as fiber, filament, yarn, fabric, oreven as a garment. Furthermore, because in many cases consumers expectto be able to wash and dry garments in machines many times, anassociated goal is to obtain garments that can withstand such repeatedmachine washing and drying while still maintaining most or all of thedesired color. Related goals include light fastness (typically withrespect to exposure to sunlight) and (using active wear as anotherexample) color stability when exposed to perspiration.

Fundamentally, the relationship between the color of a garment and itslifetime will be based upon the chemical composition of the underlyingfibers and the chemical composition of an appropriate dye composition.As is well understood in the art, a dye is technically defined as “acolorant that becomes molecularly dispersed at some point duringapplication to a substrate and also exhibits some degree of permanence.”Tortora, FAIRCHILD'S DICTIONARY OF TEXTILES, Seventh Edition, 2009Fairchild Publications.

Dye is typically categorized as either natural (e.g., from plants) orsynthetic (e.g., typically developed from other compositions usingprinciples and techniques of organic chemistry).

The dyeing characteristics of a fiber are based upon the compositionfrom which the fiber is formed. The desired property is referred to as“dyeability,” which is defined as the “capacity of fibers to acceptdyes.” (Tortora, supra).

In the manufacture or garments, it is also common to blend syntheticfibers with natural fibers in proportions that produce a finishedgarment with desired properties. For a number of reasons, blends ofcotton and polyester have long been popular. Based on that, compositionsand methods for producing dyed color in cotton-polyester blends has beenand remains a desired outcome. The natures of the two different fibers,however, present practical problems. For example, cotton can beconveniently dyed with “reactive dyes” that can be successfully added toa cotton substrate at temperatures of about 150° F.

On the other hand, the properties of polyester (i.e., the polymer formedfrom the condensation esterification and then polymerization ofterephthalic acid and ethylene glycol) required that polyester be dyedwith “disperse dyes;” i.e., small particles of colorant suspended inwater.

Coloring polyester with disperse dyes tends to require significantlyhigher temperatures; typically above 250° F. and frequently on the orderof 270° F. or higher. In many cases, high pressure (i.e., aboveatmospheric pressure) is also required to successfully dye polyester, orto reach the temperatures required to dye the polyester.

As further comparative factors, cotton dyeing tends to be driven by thepH of the dye solution or composition (typically in a basicenvironment); while polyester dyeing tends to be driven by thetemperature, and conventionally requires the addition and performance ofsupplementary chemicals commonly referred to as “carriers” or “levelingagents.” From the standpoint of economics, disperse dyes (sometimesreferred to as “high energy” dyes because of the conditions required)are more expensive than reactive dyes, and sometimes by as much as afactor of 5-10 times on a comparative basis.

Because of the differences in the dyeing compositions and the dyeingconditions, it is conventional practice to dye cotton and polyesterseparately.

In some conventional methods, blended cotton-polyester fabric is dyed intwo separate steps. In a first step, the fabric is dyed in a slightlyacidic bath at a temperature of about 270° F. or higher (e.g., using adisperse dye) in order to get the polyester to accept the dye. Thepartially dyed fabric is then scoured or rinsed, and thereafter dyed ina cotton-appropriate dye (e.g., a direct or reactive dye) at a basic pHand at a temperature of about 150° F. Because many cotton dyestuffs willdegrade at the polyester dying temperatures, the two steps cannot becombined.

As another factor that must be addressed, high dyeing temperatures tendto degrade the elasticity of stretch fibers such as spandex that areoften included in cotton-polyester fabrics and garments. Some versionsof spandex can withstand high dyeing temperatures (e.g. 270° F.), butare proportionately more expensive than versions that have essentiallythe same end-use properties, but that tend to degrade when dyed at suchhigher temperatures.

As yet another factor, perceived color (e.g., of a garment) is acombination of the interaction of light, the material the lightillustrates, and the resulting perception of the human eye. In terms oftextile dyeing, the color of the dye is based upon the functional groupsin the dye molecules. Stated differently, different colors in textilesare a function of dye molecules with different compositions. Not all dyecolors (i.e., the underlying molecules) perform, however, in the samemanner with either natural or synthetic fibers, yarns, and garments.Thus a fiber, yarn, blend, or fabric may accept certain dye colorsrelatively straightforwardly while rejecting (to some greater or lesserextent) other dye colors under the same conditions.

Furthermore, additives are often used to control or adjust theproperties of a polymer melt, and the features of such additives arelikely to change either the dyeing characteristics or the spinningcharacteristics or both.

As another factor, synthetic fibers—and certainly includingpolyester—are typically manufactured by polymerizing the startingmaterials and thereafter extruding a melt of the polymer through smallopenings in a device referred to as a spinneret; a process referred toas “spinning.” Those experienced in synthetic and natural fibers willimmediately recognize that the term “spinning” is used to refer to twoentirely different processes. In one meaning (and since antiquity)spinning refers to the step of twisting individual fibers together andpulling them into a yarn. In the manufacture of synthetic fibers, theextrusion of filaments from a melt into solidified polymer filaments isalso referred to as “spinning.” The difference is normally clear incontext. Typically, the solidification of the extruded filaments isencouraged or advanced using a quenching step, in which a carefullycontrolled airflow is directed against the extruded filaments.

The properties required of a composition that can be melt and spun inthis fashion, however, may be unrelated to, or disadvantageous incombination with, the properties that produce good dyeingcharacteristics. Composition characteristics that produce the properviscosity for spinning may be entirely unrelated, and in some casesdirectly opposite to, those properties that produced good dyeingcharacteristics. Thus, designing or adjusting the composition of apolymer, copolymer or copolymer blend to improve the spinning propertiesmay result in less desired or even unacceptable dyeing properties.

For example, in order to “spin” properly, a melted polymer must have acertain fluidity (viscosity) that permits the extrusion to producecoherent liquid filaments (i.e. that won't separate) at the spinneretwhile avoiding a viscosity that too low (“watery”) to control thespinning process for its intended purpose. Because the viscosity of apolymer melt is proportional to temperature, the degree ofpolymerization, and to other polymer properties, the spinningtemperature must be appropriate as well. Stated differently, the meltedpolymer must be able to perform at the indicated temperature.

In the context of synthetic fibers and their manufacture, the term “meltviscosity” refers to the specific resistance of the melted polymer todeformation or flow under any given conditions. The term “intrinsicviscosity” is used to describe a characteristic that is directlyproportional to the average molecular weight of a polymer. Intrinsicviscosity is calculated on the basis of the viscosity of a polymersolution (in a solvent) extrapolated to a zero concentration. Thus, theintrinsic viscosity is a characteristic that will affect the meltviscosity, but the melt viscosity is also related to other factors,particularly including the temperature of a melt.

As yet another factor, because synthetic fibers originate as a filament,they must be cut and textured (not necessarily in that order) to gainother properties that are desirable in a finished yarn, fabric, orgarment. In most cases, the texturing step requires that the syntheticfilament or fiber be mechanically or thermally formed into a shape otherthan a straight extruded filament. Accordingly, the need to texturizepolyester adds another set of properties that must be accounted for andthat may compete against the properties that enhance polymerization,spinning, or dyeing.

Thus, a need exists for polymer compositions that can produce a fiberthat can be dyed with cotton in a single step.

SUMMARY

In one aspect the invention is a composition with advantages for textilefibers. In this aspect, the invention is a melt of polyester precursorsselected from the group consisting of terephthalic acid, dimethylterephthalate, and ethylene glycol; adipic acid in an amount sufficientto give filaments and fibers made from the melt a dye receptivelysimilar to cotton at atmospheric pressure; pentaerythritol in an amountsufficient to give pill resistance to yarns blended of cotton withfibers made from the melt; and polyethylene glycol in an amountsufficient to give the melt the elasticity necessary to produce extrudedfilament from the melt. The melt is maintained at a temperature ofbetween about 285° F. and 295° F., and at an intrinsic viscosity ofbetween about 0.58 and 0.82.

In another aspect, the invention is a copolymer composition withadvantages for textile fibers. In this aspect the invention includespolyester copolymer, between about 4.5 and 5.5 percent adipic acid basedon the amount of copolymer, between about 630 and 770 parts per million(ppm) of pentaerythritol based on the amount of copolymer, and betweenabout 3.4 and 4.2 percent polyethylene glycol based on the amount ofcopolymer.

In another aspect, the invention is a method of spinning a polyestercopolymer filament. The method includes the steps of polymerizingterephthalic acid, ethylene glycol, between about 4.5 and 5.5 percentadipic acid, between about 630 and 770 ppm pentaerythritol, and betweenabout 3.4 and 4.2 percent polyethylene glycol to a copolymer melt withless than 2 percent DEG, at an intrinsic viscosity of between about 0.58and 0.82 and at a temperature of between about 285° F. and 295° F., withthe proportional amounts being based on the amount of polymerizedcopolymer, and then spinning the resulting polyester copolymer melt intofilament.

In another aspect, the invention is a method of coloring yarn blendedfrom cotton and textured polyester copolymer staple in which the yarn isbetween about 20 percent and 80 percent by weight cotton. The texturedpolyester staple has a composition of between about 4.5 and 5.5 percentadipic acid based on the amount of polyester copolymer, between about630 and 770 parts per million of pentaerythritol based on the amount ofpolyester copolymer, between about 3.4 and 4.2 percent polyethyleneglycol based on the amount of polyester copolymer, and less than 2percent diethylene glycol based on the amount of polyester copolymer.The dyeing step is carried out at atmospheric pressure and a temperaturebelow 212° F. (100° C.).

In another aspect, the invention is a blended yarn. The yarn containsbetween about 20 percent and 80 percent by weight cotton and texturedpolyester copolymer as the remainder. The textured polyester staple hasa composition of between about 4.5 and 5.5 percent adipic acid based onthe amount of polyester copolymer, between about 630 and 770 parts permillion (ppm) of pentaerythritol based on the amount of polyestercopolymer, between about 3.4 and 4.2 percent polyethylene glycol basedon the amount of polyester copolymer, and less than 2 percent diethyleneglycol based on the amount of polyester copolymer.

The foregoing and other objects and advantages of the invention and themanner in which the same are accomplished will become clearer based onthe followed detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 through 6 are color photographs of knitted fabrics that areeither control fabrics or knitted using the fibers according to thepresent invention. The photographs correspond to the data presentednumerically in Tables 3 and 4.

FIG. 7 is an enlarged isolated portion of FIG. 6 showing the differencebetween a portion of the fabric exposed to light and a portion shadedfrom light.

FIG. 8 shows a comparison of control fabrics and fabrics made from theinvention using a different levelling agent than the sample in FIGS.1-6.

DETAILED DESCRIPTION

As set forth herein, the goal of the invention is to produce a fiberthat is based upon polyester (polyethylene terephthalate) that can bedyed with cotton in a single step.

As well understood in the art, cotton is typically dyed with reactive ordirect dyes at temperatures of about 150° F. (i.e. well below theboiling point of water) and atmospheric pressure. Polyester istypically, and necessarily, dyed with dispersed dyes which require muchhigher temperatures (above 250° F. in most cases) and thus also mayrequire pressurized equipment (above atmospheric pressure conditions) inorder for the dye dispersion to penetrate the polyester. Cotton dyingtends to be sensitive to pH, while polyester typically requiresadditives referred to as carriers or leveling agents (such as fatty acidderivatives) which function to help the dye migrate throughout thesubstrate material.

In the textile art, terms such as “texturing” and “crimping,” are usedboth broadly and specifically. In the broadest sense, texturing andcrimping are used as synonyms to refer to steps in which syntheticfilament, staple fiber, or yarn is mechanically treated, thermallytreated, or both, to have a greater volume then the untreated filament,staple, or yarn. In a narrower sense, the term crimping is used todescribe the production of a two dimensional sawtooth orientation in afilament, fiber or yarn, while the term texturing is used to refer totreatments that produce looping and curling. The meaning is generallyclear in context. In the specification and claims, the word “texture” isused in a broad sense to include all possibilities for producing thedesired effect in a filament, staple fiber, or yarn.

Commonly assigned provisional application Ser. No. 61/970,569 filed Mar.26, 2014 describes compositions that include an increased amount(compared to conventional formulations) of adipic acid and diethyleneglycol (“DEG”) in order to produce a polyester that can be colored withreactive dyes. In further work with the composition, however, it hasbeen discovered that although the '569 composition can accept manycolors, it will not accept certain colors, an example of which is one ofthe NOVACRON® purple dyes from Huntsman Textile Effects (Charlotte,N.C.; Dalton, Ga.; Woodlands, Tex.). Accordingly, and without beinglimited by any particular theory, a series of comparative tests werecarried out to eliminate or moderate components in the types of formulasset forth in No. 61/970,569. On an empirical basis, these testsindicated that the higher amounts of diethylene glycol caused thefailure to uptake purple dye in acceptable amounts.

Thus, according to the invention, it has been unexpectedly determinedthat the presence of diethylene glycol in percentages above about 2%lead to problems dyeing cotton polyester blends with certain dye colorsunder cotton-favorable conditions.

Based on additional trial compositions and then dyeing and colorfastness testing, the invention provides a polyester copolymer that willdye with cotton with much better results over a wider range of colorsthan U.S. Pat. No. 6,197,0569 or other attempts. The improved copolymercan be produced by incorporating adipic acid in an amount of betweenabout 4.5 and 5.5%; pentaerythritol in an amount of between about 630and 770 ppm; between about 3.4 and 4.2% of polyethylene glycol; andwhile maintaining the amount of diethylene glycol, (a constant byproductof the esterification of terephthalic acid and ethylene glycol) at lessthan 2%. These respective amounts are all based on their proportions inthe finished copolymer.

In the most helpful composition to date, the adipic acid is present atabout 5%, the pentaerythritol at about 700 ppm, and the polyethyleneglycol at about 3.8%.

The high level (relativity) of pentaerythritol increases the reactivityof the polymerization reaction. Thus, the conventional expectation isthat a lower temperature melt is required to moderate this reactivity.In the invention, however, the pentaerythritol and the increasedreactivity are allowed to increase the intrinsic viscosity of thepolymer and the overall viscosity of the melt. Conventionally theintrinsic viscosity of polyester used for the filament and then staplefiber is kept at about 0.52-0.65. A less viscous melt tends to be too“watery” and an overly viscous melt tends to separate during extrusionfrom the spinneret (spinning).

In the invention, the intrinsic viscosity is allowed to significantlyincrease, and in particular to reach between about 0.58 and 0.82, with0.75 being exemplary. Given that conventional copolymers tend to run atlower intrinsic viscosities, the higher intrinsic viscosity of theinvention is counterintuitive.

Conventionally, in order to get a lower intrinsic viscosity polymer tospin and quench properly, the spinning temperature is reduced. Incontrast to this, the composition of the invention is allowed to spin attemperatures that are more conventional for polyester made from monomer(for example 280°-290° F. in the high polymerizer).

Thus, although the spinning temperature for a copolymer with 4.5 to 5.5percent of polyethylene glycol would conventionally be lowered to about280° F., in the invention the spinning is carried out at the sametemperature as conventional polyester monomer; e.g., about 285-290° F.

The added pentaerythritol reduces the tenacity of the resultingfilament, but in the invention this characteristic advantageous becauseit tends to reduce pilling when staple made from the filament is blendedwith cotton.

As known to those familiar with textiles in general and polyester fibersand blends of polyester and cotton in particular, the term “pilling” isused to describe small undesired entanglements of fibers (“pills”) thatcan result when the surface of a fabric is abraded (including normalwear and tear). In cotton-polyester blends, pilling can be morenoticeable because the strength of the polyester tends to preclude pillsformed from the polyester fibers from breaking off of the fabric aseasily as do pills of cotton fibers. Pilling can be tested using ASTMD3512 (“Standard Test Method for Pilling Resistance and Other RelatedSurface Changes of Textile Fabrics”) e.g., random tumble testing; orAATCC Test Method 124-2014 (“Smoothness Appearance of Fabrics afterRepeated Home Laundering”).

Table 1 illustrates a number of comparative compositions developed forthe purpose of identifying the most advantageous compositions for theinvention. Table 1 includes a series of eight (8) experiments each ofwhich was designed to produce a 1000 gram (1 Kg) batch of polymer. Thesebatches were produced in a one kilogram NCCATT reactor, following whichthe filament was spun on a laboratory scale extrusion machine. Thesestarting materials were polymerized at a temperature of 290° F. anduntil reaching a target intrinsic viscosity of 0.620.

As Table 1 indicates, the starting materials included appropriatecatalysts and at least one optical brightener (fluorescent whiteningagent). Optical brighteners are generally well understood in the art,and function by absorbing UV radiation (e.g., in the region from 360 to380 nanometers) and re-emitting longer-wavelength, visible blue-violetlight in the visible portion of the spectrum. Such compositions can beselected by the skilled person without undue experimentation, andprovided that the selected brightener does not undesirably affect thedesired properties of the finished copolymer, fiber, or fabrics. Thestarting materials also included small amounts of antimony oxide (0.35g), 0.02 g of 10% phosphoric acid, and tetramethyl ammonium hydroxide(0.160 g of a 5% solution in water).

TABLE 1 Production of 1000 gram batches of copolymer Units PD11 PD12PD13 PD14 PD15 PD16 PD17 PD18 TA Grams 861 828 828 828 828 828 828 828EG ml 406 391 391 391 391 391 391 391 Sb₂O₃ Grams 0.3 0.3 0.3 0.3 0.30.3 0.3 0.3 Cobalt Grams 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 AcetateTiO₂ Grams 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 OB Grams 0.2 0.2 0.2 0.2 0.20.2 0.2 0.2 PEG ml 0.0 38.0 38.0 38.0 30.0 30.0 22.0 22.0 (MW = 400)Note 1 DEG ml 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Adipic Grams 50.050.0 50.0 50.0 50.0 30.0 50.0 50.0 Acid Penta- Grams 0.9 1.0 0.7 0.5 0.70.7 0.7 0.9 erythritol Total of Grams 1242.5 1240.6 1240.3 1240.1 1242.31222.3 1239.3 1239.4 Raw Materials TA = terephthalic acid; EG = ethyleneglycol; DEG = diethylene glycol; PEG = polyethylene glycol; OB = opticalbrightener Note 1: add after esterification & before polymerization

Fabrics formed from the compositions in Table 1 can be dyed in thefollowing generally conventional manner. The fabric to be dyed is placedin an aqueous solution that optionally includes desired auxiliaries(e.g., leveling agents and salt) and allowed to equilibrate as thetemperature is raised from room temperature to the dyeing temperature(e.g. above about 150° F., but below boiling) over the course of about25 minutes. The temperature is then maintained generally constant whilethe dye is added (in a liquor ratio of about 10:1) over a period ofabout 15 minutes, after which the temperature is raised to about 195° F.for about 30 minutes to allow the dye to migrate. The temperature isthen lowered over an interval of about 10 minutes to about 158° F. andmaintained there for about 35 minutes to allow the dye to fix.

The dyed fabric is then rinsed for about 10 minutes at about 122° F.,and potentially rinsed more than once depending upon the overallcircumstances. The fabric is then neutralized for about 10 minutes atabout 160° F., typically with weak acetic acid (e.g., no more than 1%).The fabric can then be soaped for 10 minutes for one or two cycles atabout 200° F., depending upon the hardness of the water and the shade ofthe intended color.

The fabric is then rinsed with hot water (about 160° F.) and then coldwater, each for about 10 minutes. If desired or necessary (e.g.,depending upon the dye shade or other factors) the fabric can be treatedwith fixatives (e.g., polymeric quaternary ammonium compounds areexemplary) and softeners.

Of these compositions, PD11 would accept a high energy dye at 260-270°F., but would not accept a low energy dye at 205° F. PD12 and PD13,however, would accept a low energy dye throughout the fiber. Thecapacity to dye properly with a low energy dye provides significant costsavings because high-energy dyes are proportionately more expensive(sometimes by a factor of 10) than reactive dyes.

Although the invention is not limited by any particular theory, it canbe hypothesized that the adipic acid provides the dye receptivity, thepentaerythritol provides the pill resistance, and the polyethyleneglycol provides the elasticity to spin the melt into filament.

Accordingly, it will be understood that in one aspect the invention isthe composition: polyester, adipic acid, pentaerythritol, polyethyleneglycol, or low amounts of diethylene glycol. In turn, the compositioncan be understood as a polymerized melt, as a polyester copolymerfilament made from the melt, or as a textured filament made from thecomposition.

Texturing is well understood in the art and will not be otherwisedescribed in detail, other than to point out that to date, thecomposition of the invention produces filament that can be texturedusing conventional steps (e.g., heat setting while in a twistedposition).

The composition aspects of the invention also include the manufacture ofstaple fibers cut from the filament (typically from a texturedfilament), yarns, particularly blends of cotton and the polyestercopolymer of the invention, dyed yarns, fabrics, dyed fabrics, andgarments.

It will further be understood that the dying step can be carried out onthe blended yarn, on a fabric formed from the blended yard, or even on agarment formed from the blended yarn.

In the method context, the invention includes the steps of polymerizinga charge of terephthalic acid, ethylene glycol, adipic acid in an amountof between about 4.5 and 5%, pentaerythritol in an amount of betweenabout 630 and 770 ppm, polyethylene glycol in an amount of between about3.4 and 4.2%, and less than 2% diethylene glycol. These amounts areexpressed as the weight percentage of the component as compared to thetotal weight of the finished copolymer.

The charge is run at (or until it reaches) an intrinsic viscosity ofbetween about 0.68 and 0.82 and at a temperature of between about 285and 295° F. The melt is spun into filament in an otherwise conventionalprocess.

The filament produced by the method can be textured and cut into staplefiber, spun into a blended yarn with cotton (typically with cotton inthe range of 5-95% by weight) and dyed as yarn. Alternatively, theblended yarn can be woven or knitted into fabric and then dyed and thenformed into a garment. In some circumstances, the dyeing step will becarried out on the garment, but dyeing the yarn is probably most common.

Those skilled in the art will also appreciate, however, that thefilament can be used as a yarn (“filament yarn”); i.e., without beingcut into staple or without being blended with another fiber (e.g.,cotton). Such filament yarns are particularly advantageous in the activewear industry. In particular, filament yarn according to the inventionprovides the opportunity to use spandex that can be dyed at theinventive dyeing temperatures (about 205° F.) while maintaining all ofthe desired spandex properties. As set forth in the background,variations of spandex that can be dyed at high temperature areavailable, but at higher cost, and without any corresponding stretch orrecovery advantages for active wear purposes.

Because poly-cotton blends are manufactured, sold, and used in a varietyof proportions, a potentially wide range (5-95% cotton) is expressedherein. Nevertheless, it will be understood that although the inventioncertainly offers advantages for high cotton blends, the inventionprovide particular advantages for poly-cotton blends with a largerproportion (50% or more) of polyester.

As noted previously, with respect to the composition, in the methodsteps, the best results to date have been obtained with about 5% adipicacid, about 700 ppm pentaerythritol and about 3.8% polyethylene glycol,all based on the total weight of the copolymer composition.

In another aspect, the invention can be considered as the method ofdying a blended yard formed from cotton and textured polyester staplethat starts with the composition described herein. Thus, the dyeing stepis carried out on a yarn that includes between about 5 and 95 percent byweight cotton, along with the polyester that includes the amounts ofadipic acid, pentaerythritol, polyethylene glycol, and diethylene glycolrecited with respect to the composition and the method of making thefilament.

In another aspect, the invention is the blended yarn itself containingabout 5-95% by weight cotton, with the textured polyester as theremainder. The textured polyester has the composition described withrespect to the other embodiments. For the sake of completeness these areabout 4.5-5.5% adipic acid (5% exemplary), between 630 and 770 ppm ofpentaerythritol (700 ppm exemplary), between about 3.4 and 4.2%polyethylene glycol (3.8% exemplary) and less than 2% of the diethyleneglycol byproduct. Again, these amounts are based on the weight of thefinished copolymer.

As with the other embodiments, the yarn can be dyed, and formed intofabric and garments with the dyeing being carried out on the blend asopposed to the conventional steps of dyeing cotton separately frompolyester.

Thus, using the invention, a blended fabric can be successfully dyedusing a single dye. Alternatively, if two dyes are preferred, theinvention allows both dyestuffs to be maintained in a single bath, thuseliminating the conventional rinsing or scouring step between a dispersedyeing step for the polyester and a direct dyeing step for the cotton.In turn, the invention provides the advantages of less water used andless effluent produced.

On a production or continuous scale, the invention is expected to beformed and used in steps with which the skilled person is quitefamiliar. Thus, as a predictive example, the terephthalic acid andethylene glycol are mixed into a paste (or slurry) at a mole ratio ofbetween about 1:1 and 1.2:1 (TA to EG). The paste is then transferred toa primary esterifier (“PE”) under above atmospheric pressure andtemperatures above 250° C. (typically 260-280° C.). The compositionforms the esterified monomer (usually representing about 90 percentesterification). This product is then transferred to a secondaryesterifier, at which point the pentaerythritol and adipic acid can beadded. Pressures in the secondary esterifier are lower than the primaryesterifier, but temperatures are slightly higher; e.g., 270-275° C., andesterification reaches (for example) about 94%.

The esterified composition is then transferred to the low polymerizer,and if desired the pentaerythritol and adipic acid alternately can beadded between the secondary esterifier and the low polymerizer. The lowpolymerizer operates at a temperature of about 275-280° C., and under avacuum to remove the water vapor (the polymerization is a condensationreaction) and the monomers reach a degree of polymerization of about75-100. The composition is then transferred to a high polymerizer wherepolymerization reaches much higher numbers, typically on the order of20,000 units.

The high polymerizer typically runs at temperatures of about 270°-310°C. for standard PET polymers with 285°-290° C. being particularlyrepresentative. Conventional copolymers that contain polyethylene glycolnormally would be run at temperatures lower in this range; e.g., about280° C. In the invention, however, the temperature can be maintainedhigher (e.g., 285°-290° C.) within the standard range but the intrinsicviscosity is allowed to reach between about 0.58 and 0.82, with about0.75 being favored in many circumstances.

Intrinsic viscosity is typically measured in a capillary viscometerusing a sample of the polymer dissolved in an appropriate solvent. As analternative, instruments are available that can measure the intrinsicviscosity directly and without the step of dissolving the polymer in asolvent. The intrinsic viscosities described herein can be measured orconfirmed using, for example ASTM D5225 (“Standard Test Method forMeasuring Solution Viscosity of Polymers with a DifferentialViscometer”) or any test or instrument that gives the same resultswithin an acceptable tolerance or margin of error.

With respect to the invention (and in many cases in general) colorfastness represents the resistance of a dyed color to fading or bleedingunder various types of influences on the yarn, fabric, or garment.Exposure to water, light, rubbing, washing, and perspiration aretypical. Color fastness testing seeks to identify the properties of thematerial in a manner that is helpful and reproducible.

In a typical test, (AATCC Test Method 61-2013; Colorfastness toLaundering: Accelerated) the fabric color loss and surface changesresulting from detergent solution and abrasive action of five typicalhand or home launderings, with or without chlorine, are roughlyapproximated by one 45 minute test. Samples are exposed to conditions oftemperature, detergent solution, bleaching and abrasive action that areexpected to produce a color change representative of five hand or homelaunderings. Standard tests have also been developed by the Society ofDyers and Colorists (SDC; www.sdc.org.uk; accessed Jul. 24, 2015) andthe International Organization for Standardization (ISO; www.iso.org;accessed Jul. 24, 2015).

Light fastness (i.e., color fastness under exposure to light) can alsobe carried out using a high energy xenon fadometers under definedconditions of radiation intensity cycle time (light and dark) andtemperature. AATCC Test Method 169-2009, “Weather Resistance ofTextiles: Xenon Lamp Exposure,” is an appropriate test.

The resulting color differences can be evaluated using standardized grayscale and gray scale testing methods (e.g., ASTM D2616-12; “StandardTest Method for Evaluation of Visual Color Difference With a GrayScale”).

TABLE 2 PD 13 Pill Testing Nov. 30, 2015 RTP Test at FRC 30 min 60 mincontrol 40A 20/1 50/50 KPOE 222 111 PD 13 20/1 50/50 KPOE 333 333control 40A 20/1 100% OE 333 222 PD 13 20/1 100% OE 333 333 3HL Test atDelta 3HL control 40A 20/1 50/50 KPOE 3.5 PD 13 20/1 50/50 KPOE 3.0control 40A 20/1 100% OE 2.5 PD 13 20/1 100% OE 2.5

Table 2 gives the results of random tumble pilling (“RTP”) and homelaundering (“HL”) tests for both control fabrics and fabrics made fromthe present invention. As indicated in Table 2, the PD 13 formulationfrom Table 1 was used as the synthetic component representative of theinvention. Testing was carried out using ASTM RTP and ASTM D3512 HL(http://www.astm.org/Standards/D3512.htm; accessed Mar. 3, 2016). Thetests are available on a subscription basis, but generally consist of astandardized rubbing action applied between a sample fabric and astandard fabric. A particular number of rubs are carried out, followingwhich the samples are examined to determine the number of pills created.The fabrics are placed on rectangular blocks to carry out the rubbingmotion.

In Table 2, 20/1 is the English cotton count (“cotton yarn countsystem,” Totora, supra). Some of the fabrics were 50/50 blends of cardedcotton and synthetic staple fibers, open end spun, with the syntheticbeing either the invention (PD 13) or a Dupont AKRA control (DuPont-AkraPolyester, LLC, Charlotte, N.C. 28210, USA). Other fabrics were formedfrom either 100% staple according to the invention or (for control) 100%of the Dupont AKRA polyester. According to a material safety data sheetfrom DuPont (MSDS No. DU005415), the composition is polyethyleneterephthalate (Charlie Alpha Sierra number 25038-59-9) which may includea spin finish of between about 0.2 and 3% of lubricant, and less than 5%of titanium dioxide.

The third and fourth columns represent the timing of the test beforevisual inspection, along with the rating of the fabric each time, withhigher numbers being better in the industry.

The home laundering testing indicated that the control and the inventionwould be judged equivalent from a visual standpoint, or with the controlbeing slightly better in one case. Nevertheless, and although admittedlya subjective determination, the invention is commercially equivalent tothe control for all practical purposes and provides the other advantagesdescribed herein.

The blended fabrics in FIGS. 3-6 were dyed using a one-bath-two-stepdyeing process that significantly saves both resources and energy. Insuch a dying process, water and disperse dye (for the polyester) andreactive dye (for the cotton) are all added together to form the dyesolution. In the first step, a weak acid (typically acetic) is added tobring the pH to between about 5.5 and 6.5. The mixture is then heated toa temperature of about 205° F.; i.e., a temperature at which theinventive polyester will dye, but standard polyester will not.

In a second step in the same bath—which is not possible with standardpolyester—salt and caustic (i.e., a base, typically sodium hydroxide,NaOH) are added to the same bath to activate the reactive cotton dye andbring the pH to the basic side (e.g. about 8).

This one bath two-step process avoids of the need to empty the dyevessel (“pot”) after the polyester dying step and to refill it for thecotton dying step. At a minimum this provides a significant time savingswhich becomes cumulatively advantageous for repeated dyeing steps.Secondly, because the temperature of the bath can be the same for boththe cotton and polyester dyeing steps, less heating is required, as isthe time required for re-heating. The result is a fully dyed blendedfabric from the single dye bath.

TABLE 3 140575 Internal-Parkdale Light Fastness 11-12-15.txt Method:Change of shade (ISO 105-A05) Task Id (Standard): Internal-Parkdale 2015Task Id (Samples): Internal-Parkdale 2015 Sample: dEF Rating Standard:140575 # 101315A ctrl 140575 #101315A 20 hrs 2.79 3-4 140575 #101315A 40hrs 4.28 2-3 140575 #101315A AcidPersp/20 hr 2.84 3-4 140575 #101315AAlkPersp/20 hr 2.68 3-4 Standard: 140575 # 101315B ctrl 140575 #101315B20 hrs 5.58 2-3 140575 #101315B 40 hrs 8.65 1-2 140575 #101315BAcidPersp/20 hr 4.87 2-3 140575 #101315B AlkPersp/20 hr 5.18 2-3Standard: 140575 # 101415 ctrl 140575 #101415 20 hr 3.32 3 140575#101415 40 hr 5.81 2 140575 #101415 AcidPersp/20 hr 5.74 2-3 140575#101415 AlkPersp/20 hr 4.29 2-3 Standard: 140575 # 101515 ctrl 140575#101515 20 hrs 3.70 3 140575 #101515 40 hrs 6.07 2 140575 #101515AcidPersp/20 hrs 6.14 2 140575 #101515 AlkPersp/20 hrs 4.48 2-3Standard: 140575 # 101615 ctrl 140575 #101615 20 hrs 4.91 2-3 140575#101615 40 hrs 8.24 1-2 140575 #101615 AcidPersp/20 hrs 5.17 2-3 140575#101615 AlkPersp/20 hrs 5.53 2-3 Standard: 140575 # 102215 ctrl 140575#102215 20 hrs 3.87 3 140575 #102215 40 hrs 6.88 2 140575 #102215AcidPersp/20 hrs 6.17 2 140575 #102215 AlkPersp/20 hrs 5.03 2-3

Tables 3 and 4 are best interpreted as follows. The sample fabrics inthe tables correspond to a lot number in the upper left-hand corner ofeach of FIGS. 1-6 (e.g., “101315A” for FIG. 1). As a key:

FIG. 1 101315A FIG. 2 101315B FIG. 3 101415 FIG. 4 101515 FIG. 5 101615FIG. 6 102215

To help clarify the photographs, in each of FIGS. 1 to 6 the followingreference numerals correspond to the following results: 10-2A wash;11-3A wash; 12—dry crock; 13—wet crock; 14—cold water bleed; 15—acidperspiration; 16 alkaline perspiration; 17-20 hour lightfastness; 18-40hour lightfastness; 21 acid perspiration light fastness; 22 alkalineperspiration lightfastness; 23—(for the blended fabrics in FIGS. 3-6) asample of fabric color after cotton has been removed (typically by“burning” it out with sulfuric acid, H₂SO₄).

Table 3 is a combination of six sub-tables which provide test resultsfor each of the six different fabrics illustrated in FIGS. 1 through 6.Thus, the first sub-portion gives the results for 101315A for a 20 hourlightfastness test (ISO 105 A05), then a 40 hour lightfastness test,then a 20 hour acid perspiration test, and then 20 hour alkalineperspiration test.

The second sub-portion of Table 3 corresponds to FIG. 2 (101315B); andthereafter FIG. 3 (101415); FIG. 4 (101515); FIG. 5 (101615); and FIG. 6(102215).

In each case the dEF rating is calculated under ISO 105-A05. In general,ISO 105-A05 is an instrumental test for assessing the color change of atest specimen in comparison to the color change of a control specimenfollowed by a series of calculations that convert the instrumentmeasurements into a grey scale rating.

The light fastness test is proprietary to the International StandardsOrganization, but publicly available (i.e. not confidential) on asubscription basis. In general, the color coordinates for lightness(L*), Croma (C*) and Hue H_(AB) are measured for control and testspecimens, and the differences are calculated and converted to the dEFgrayscale rating by using equations that form part of the test protocol.

TABLE 4 140575 - Internal Parkdale Fastnes Results 101615 101415 102215101515 101315A 101315B 2A CA 4 3.5 4 4 3.5 4 CO 5 5 5 5 5 5 PES 4 3.5 44 3.5 4 PA 5 5 5 5 5 5 PAC 5 5 5 5 5 5 WO 5 5 5 5 5 5 3A CA 3 3 3 3 3 3CO 4 4.5 4 4 4.5 4 PES 3 3 3 3 3 2.5 PA 4 4.5 4 4 4.5 4 PAC 4 4.5 4 44.5 4 WO 4 4.5 3.5 3.5 4.5 3.5 Cold Water Bleed CA 5 5 5 5 5 5 CO 5 5 55 5 5 PES 5 5 5 5 5 5 PA 5 5 5 5 5 5 PAC 5 5 5 5 5 5 WO 5 5 5 5 5 5 AcidPerspi- ration CA 5 5 5 5 5 5 CO 4 5 5 5 5 5 PES 5 5 5 5 5 5 PA 5 5 5 55 5 PAC 5 5 5 5 5 5 WO 5 5 5 5 5 5 Alkaline Perspi- ration CA 5 5 5 5 55 CO 4.5 5 5 5 5 5 PES 5 5 5 5 5 5 PA 5 5 5 5 5 5 PAC 5 5 5 5 5 5 WO 5 55 5 5 5

Table 4 summarizes similar results for five types of tests: 2A washfastness (AATCC 61 CAN/CCSB & ISO 105-006 Test No BIM), 3A wash fastness(AATCC 61 CAN/CCSB & ISO 105-006 Test No BIM), cold water bleed(steeping the fabric for a defined interval in water at 25° C.), acidperspiration fastness: (ISO 105-E04), and alkaline perspiration fastness(ISO 105-E04).

The sample fabrics (corresponding to FIGS. 1-6) are listed as a headerrow for each of the five sub-tables, as against a column that representscellulose acetate (CA), cotton (CO), polyester (PES), nylon (PA),acrylic (PAC), and wool (WO). These are the fabrics in the strips in thecorresponding portions of the photographs of FIGS. 1-6. The resultsindicate the potential color stability of the fabric when a fabric isformed of a blend of the invention and any one or more of these othertypes of fibers.

In the same way that the photographs illustrate excellent results withrespect to (fabrics), the comparison testing of Table 4 confirms theresults. The values are those obtained from ISO-C06.

Other tests used or useable to identify and compare the properties ofthe invention include one or more of the following.

AATCC 61 is a test developed by the American Association of TextileChemists and Colorists (Research Triangle Park North Carolina USA). Thedetails of the test are available from the association atAATCC.org/test/methods/test-method-61/; accessed Mar. 3, 2016.

The test evaluates the colorfastness with respect to laundering oftextiles that are expected to withstand frequent laundering. Specimensare tested “under appropriate conditions of temperature, detergentsolution, bleaching and abrasive action such that the color change issimilar to that occurring in five hand or home launderings.

The shrinkage test is AATCC 135. Again this is proprietary in itsdetails, but generally consists of marking a sample section of thefabric at selected measured distances, laundering the fabric in apredetermined manner, including drying, and then re-measuring theposition of the marks to determine the amount of shrinkage.

Crocking (AATCC 8) is used to determine the amount of color thattransfers from one sample fabric to another fabric by rubbing. Thesample fabric to be tested is fastened to a crock meter and then rubbedagainst a white test cloth. The test is carried out both with a dry testcloth and then a wet test cloth. The amount of color transferred to thetest cloth is assessed by comparison with the AATCC chromatictransference scale. The details of the test are proprietary to AATCC,but are publicly available and well understood by the skilled person.

The fabrics were also tested under AATCC skewing (skew, skewness) testmethod 179 which again is proprietary to AATCC, but publicly availableand well understood in the art. The test determines the change inskewness in woven and knitted fabrics, or twisting garments whensubjected to testing that mimics repeated automatic launderingprocedures commonly used in home laundering. The test defines particularwashing and drying procedures for obtaining the measured results. Tosome extent skewness testing gives an indication of the degree to whichthe yarns or courses in a fabric will be distorted from their intendedand manufacture design.

Colorfastness with respect to commercial and domestic hot laundering canalso be determined using ISO test number 105-006. The exact testapparatus, materials and reagents and procedures are proprietary to theInternational Standards Organization (web address), but again arepublicly available (subscription or individual purchase cost) and wellunderstood by the skilled person.

Related tests deal with perspiration fastness (ISO 105-E04) waterfastness (ISO 105-E01); and light fastness (ISO 105-B02).

In general, perspiration testing is carried out using two standardsolutions that mimic perspiration, but with one being slightly acidic(e.g., pH 5.5) and one being slightly basic (e.g. pH 8.0).

A sample of a fabric to be tested is placed in immediate contact (oftenby sewing them together) with an undyed fabric that is otherwiseidentical. This composite sample is then soaked in the acidic or basicsolution for about 30 minutes, and then maintained at an elevatedtemperature (for example 35-39° C.) under a slight pressure for aboutfour hours.

The complementary tests (acid or base) are carried out in exactly thesame manner. The composite samples can then be separated from the whitecloth and dried, and the change in color of the specimen and thestaining of the white cloth can be compared against a standardize grayscale.

FIG. 8 illustrates results from a subgroup of tests carried out onfabrics (control and invention) dyed using leveling agents differentfrom those selected for the samples in FIGS. 1-6.

In FIG. 8, six different fabrics are illustrated (and numbered) alongthe top row: Dacron dyed using 1% Univadine DLS (25); the invention dyedusing 1% Univadine DLS (26); Dacron dyed in 1% Univadine DFM (27); theinvention dyed in 1% Univadine DFM (30); Dacron dyed in 10% UnivadineDFM (31); and the invention dyed in 10% Univadine DFM (32). TheUnivadine leveling agents are available from Huntsman Textile Effects3400 Westinghouse Boulevard Charlotte, N.C. 28273 USA

The middle row shows dye residue results based on six undyed Dacronsamples each of which was placed in the dye bath after the dying step.To the extent that the original fabrics (25-27 and 30-32) failed touptake dye efficiently, the results are indicated in the second row. Onthis basis, less colored results are better than the results with faint(or even predominant) color.

Accordingly these show the residual dye uptake with the correspondingrelationships: 25 and 33; 26 and 34; 27 and 35; 30 and 36; 31 and 37;and 32 and 40.

Test sheets 33, 35 and 37 all show evident color indicating thatresidual dye remained after Dacron samples 25 27 and 31 were dyed. Testsheets 34, 36 and 40 are essentially white, indicating a much moresuccessful dye uptake by the inventive fabric samples 26, 30 and 32respectively.

The bottom row of FIG. 8 shows light fastness test results made on thesame fabrics for the same comparative purposes. In this row, therelationships are In each case, the fabric formed from the inventivecomposition gives superior results to the Dacron standard.

In the specification there has been set forth a preferred embodiment ofthe invention, and although specific terms have been employed, they areused in a generic and descriptive sense only and not for purposes oflimitation, the scope of the invention being defined in the claims.

1. A method of spinning a polyester copolymer filament comprising thesteps of: polymerizing terephthalic acid, ethylene glycol, between about4.5 and 5.5 percent adipic acid, between about 630 and 770 ppmpentaerythritol, and between about 3.4 and 4.2 percent polyethyleneglycol to a copolymer melt with less than 2 percent DEG; at an intrinsicviscosity of between about 0.58 and 0.82 and at a temperature of betweenabout 285° F. and 295° F.; with the proportional amounts being based onthe amount of polymerized copolymer; and spinning the resultingpolyester copolymer melt into filament.
 2. A method further comprisingtexturing the filament produced by the method of claim
 1. 3. A methodaccording to claim 2 further comprising cutting the textured filamentinto staple fiber.
 4. A method according to claim 3 further comprisingspinning the polyester staple with cotton to form a blended yarn.
 5. Amethod according to claim 4 further comprising dyeing the blended yarn.6. A method according to claim 5 further comprising dyeing the yarn witha reactive dye at atmospheric pressure.
 7. A method according to claim 4further comprising forming a fabric from the yarn of claim
 37. 8. Amethod according to claim 7 further comprising dyeing the fabric fromclaim
 40. 9. A method according to claim 8 further comprising dyeing thefabric with a reactive dye at atmospheric pressure
 10. A methodaccording to claim 8 further comprising forming a garment from the dyedfabric of claim
 8. 11. A method according to claim 5 further comprisingforming a fabric from the yarn of claim
 5. 12. A method according toclaim 7 further comprising forming a garment from the fabric of claim 7.13. A spinning method according to claim 1 comprising: polymerizingterephthalic acid, ethylene glycol, 5 percent adipic acid, andpentaerythritol to a copolymer melt with about 3.8 percent PEG, lessthan 2 percent DEG, an intrinsic viscosity of about 0.75 and at atemperature of between about 285° F. and 295° F.
 14. A filament producedby the method of claim
 13. 15. A textured staple fiber made from thefilament of claim
 14. 16. A yarn blended from cotton and the texturedstaple formed from the extruded filament made from the composition ofclaim
 13. 17. A fabric formed from the blended yarns of claim
 16. 18. Amethod of coloring yarn comprising: dyeing a yarn blended from cottonand textured polyester copolymer staple; wherein the yarn is betweenabout 20 percent and 80 percent by weight cotton; and wherein thetextured polyester staple has a composition of between about 4.5 and 5.5percent adipic acid based on the amount of polyester copolymer, betweenabout 630 and 770 parts per million (ppm) of pentaerythritol based onthe amount of polyester copolymer, between about 3.4 and 4.2 percentpolyethylene glycol based on the amount of polyester copolymer, and lessthan 2 percent diethylene glycol based on the amount of polyestercopolymer; and carrying out the dyeing step at atmospheric pressure anda temperature below 212° F. (100° C.).
 19. A method according to claim18 further comprising knitting the yarn into a fabric.
 20. A methodaccording to claim 19 comprising forming a garment from the knittedfabric.
 21. A method according to claim 18 further comprising weavingthe yarn into a fabric.
 22. A method according to claim 19 comprisingforming a garment from the woven fabric.
 23. A method according to claim18 comprising dyeing a yarn in which the polyester staple has acomposition of about 5 percent adipic acid based on the amount ofpolyester copolymer, about 700 parts per million (ppm) ofpentaerythritol based on the amount of polyester copolymer, about 3.8percent polyethylene glycol based on the amount of polyester copolymer,and less than 2 percent diethylene glycol based on the amount ofpolyester copolymer.
 24. A method according to claim 18 comprisingdyeing the yarn with a reactive dye.
 25. A method according to claim 18comprising dyeing the yarn with a disperse dye.